Phenyl (phenoxy or phenylthio) azolomethanes

ABSTRACT

Disclosed are aryl(aryloxy or arylthio) azolomethanes, their preparation and their pesticidal and plant growth regulation uses.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division of application Serial No. 653,399, filed Sept. 24,1984, now U.S. Pat. No. 4,636,514 issued Jan. 13, 1987, which is acontinuation of Ser. No. 407,852, Aug. 13, 1982, now abandoned.

SUMMARY OF THE INVENTION

The present invention is directed to aryl(aryloxy orarylthio)azolomethanes corresponding to the formula ##STR1## wherein Rrepresents hydrogen, phenyl or pyridyl;

R¹ represents phenyl, pyridyl or thienyl;

R² represents phenyl or pyridyl;

R³ represents a 5-membered N-heterocyclic ring of the formula ##STR2##wherein each Z independently represents --CH or N and at least one of Zis N; X is C₁ -C₄ alkyl, Br, Cl, F or I and n represents an integer offrom 0 to 3 and

Y is oxygen or sulfur.

In the present specification and claims, the terms "phenyl", "pyridyl"or "thienyl" are employed to designate both unsubstituted as well asphenyl, pyridyl or thienyl groups which are substituted independentlywith from 1 to 2 to 3 bromo, chloro, fluoro or iodo, C₁ -C₄ alkyl, C₁-C₄ alkoxy, NO₂, --CN or CF₃ groups. The substitutions can be the sameor different. The terms "alkyl" and "alkoxy" as employed hereinrepresent straight, branched chain or cyclic alkyl or alkoxy groups. Itis to be noted that all substituent groups are sterically compatiblewith each other.

In the present specification and claims, the term "stericallycompatible" is employed to designate X and Z substituent groups whichare not affected by steric hindrance as defined in "The CondensedChemical Dictionary", 7th edition, Reinhold Publishing Co., N.Y., page893 (1966) which definition is as follows: "steric hindrance. Acharacteristic of molecular structure in which the molecules have aspatial arrangement of their atoms such that a given reaction withanother molecule is prevented or retarded in rate."

Steric hindrance may be further defined as compounds having substituentswhose physical bulk does not require confinement within volumesinsufficient for the exercise of their normal behavior as discussed in"Organic Chemistry" D. J. Cram and G. Hammond, 2nd edition, McGraw-HillBook Company, N.Y., page 215 (1964).

The aryl(aryloxy or arylthio)azolomethanes of the present inventionpossess excellent pesticidal properties and are very useful for thecontrol of various fungal or insect pest. In addition various compoundshave been found to have plant growth regulation activity (enhancement,stunting or killing).

The azolomethane compounds of the present invention are crystallinesolids or liquids which are sparing soluble in water and which aresoluble in most organic solvents.

The azolomethane compounds of the present invention can be preparedemploying a variety of methods.

METHOD A

Substantially equimolar amounts of a dihalomethyl compound correspondingto the formula ##STR3## a phenol or thiophenol of the formula

    HYR.sup.2

and a N-heterocyclic compound reactant HR³ which corresponds to theformula ##STR4## are reacted together in the presence of a solvent and astrong base. Representative of such bases include sodium hydride andpotassium tertiary butoxide.

The reaction scheme is as follows: ##STR5## In the above R, R¹, R² andR³ is a hereinabove defined and Me is alkali metal. No attempt has beenmade to present a balanced equation.

The reaction is conveniently carried out in an inert solvent whichserves as a carrier medium. Representative inert solvents operable inthe present invention include 1,2-dimethoxyethane, dimethylformamide(DMF), dimethylsulfoxide (DMSO) and the like. The amount of thereactants employed is not critical; ordinarily, essentially equimolarproportions of each reactant is employed. The reaction takes placesmoothly at temperatures of from about 20° to about 200° C.; however,the reaction is preferably carried out at temperature of from about 80°to about 130° C. While the reaction can be conducted over a wide rangeof pressures, no particular advantage ordinarily results from the use ofsub- or super-atmospheric pressures and the reaction is thereforeordinarily carried out under ambient pressure conditions.

In carrying out the reaction, the reactants are contacted in anyconvenient fashion and the resulting reaction mixture is agitated in thereaction temperature range for a period of time sufficient to assuresubstantial completion of the reaction. The reaction time period, whichvaries from about 15 minutes to about 24 hours, is dependent upon thereaction temperature employed as well as the nature of the raw materialreactants employed. Generally, the reaction time period ranges fromabout 1 to about 8 hours.

Following the completion of the reaction, the reaction mixture is cooledto room temperature, mixed with water and solvent extracted. The extractis washed with a mild aqueous basic solution, dried and the carriermedium removed in vacuo to obtain the product. The product can befurther purified by conventional procedures such as recrystallization,solvent extraction, distillation, chromatography and the like.

In a preferred operation, the N-heterocyclic reactant is added to astirring mixture of the alkali metal hydride in the solvent and then thephenol or thiophenol reactant is added. After hydrogen evolution ceases,the ##STR6## reactant is added and the mixture stirred at the reactiontemperature until the reaction is complete. The product is recovered inthe manner set forth above.

METHOD B

Substantially equimolar amounts of a methane compound corresponding tothe formula ##STR7## is brominated with a conventional brominating agentsuch as, for example, N-bromosuccinimide (NBS) in the presence of asolvent and a catalyst. The resulting product is then reacted with asubstantially equimolar amount of the N-heterocyclic reactant HR³ in thepresence of a solvent and a HB absorber.

The reaction scheme is as follows: ##STR8## wherein R, R¹, R² and R³ areas hereinabove defined. No attempt has been made to present a balancedequation.

After the completion of the reaction, the reaction mixture is filteredand the solvent removed. The product is then recovered from the residuevia preparative high pressure liquid chromatography. If desired theproduct can be further purified by solvent recrystallization.

In carrying out this reaction, the methane compound is brominated byreacting it with a substantially equimolar amount of a brominating agentsuch as N-bromosuccinimide in a solvent, such as for example, carbontetrachloride or chloroform.

Representative HBr absorbers include, for example, sodium or potassiumcarbonate, triethylamine, 2,6-dimethylpyridine or1,5-diazabicyclo[3.4.0]nonene-5(DBN).

A catalyst is normally employed in catalytic amounts of from about 0.1to about 20 mole percent. Representative catalyst includedibenzoylperoxide, ditertiarylbutylperoxide or azobis isobutyronitrile.

The reaction is usually carried out under ultraviolet irradiation suchas from a conventional sun-lamp. The reaction is initiated by heatingthe reaction mixture until a vigorous exothermic reaction starts. In asmall scale operation, it is convenient to do such heating with a heatgun.

At the completion of the bromination reaction the reaction mixture isimmediately cooled to a temperature in the range of from about -10° toabout 25° and any insolubles are removed by filtration or otherconventional separation procedures. The so recovered mixture is thenreacted with the N-heterocyclic reactant in the presence of an HBrabsorber such as, for example, sodium, potassium, calcium or lithiumcarbonate.

This reaction is conveniently carried out at room temperature thoughtemperatures from about -20° to about 75° C. can be employed. At thecompletion of this reaction, the reaction mixture is filtered to removeany insolubles and then the solvent is removed product can be recoveredfrom the residue by conventional techniques including preparative highpressure liquid chromatography or solvent recrystallization. If furtherpurification of the product is desired, it may be recrystallized from asolvent such as ethyl ether or pentane or mixtures thereof.

DESCRIPTION OF SOME PREFERRED EMBODIMENTS

In order that the present invention may be more fully understood, thefollowing examples are given primarily by way of illustration and shouldnot be construed as limitations upon the overall scope of the presentinvention.

Example I3-((2,4-Dichlorophenoxy)-1H-1,2,4-triazole-1-yl-methyl)pyridine ##STR9##

To a stirred mixture of 3.36 grams (g) (0.14 moles (m)) of sodiumhydride in 150 milliliter (ml) of dimethylsulfoxide (DMSO) was slowlyadded 5.18 g (0.075 m) of 1H-1,2,3-triazole and then 11.41 g (0.07 m) of2,4-dichlorophenol. After hydrogen evolution had ceased, 11.34 g (0.07m) of 3-(dichloromethyl)pyridine was added thereto and the resultingmixture was stirred at 80°-90° C. for seven (7) hours. The mixture wascooled to room temperature (25° C.) and then poured into 1000 ml ofwater. The resulting mixture was extracted with ethylether (3extractions each with 300 ml portions of ether). The extracts werecombined and washed with 5 percent (%) aqueous sodium hydroxide, driedover magnesium sulfate and the solvent removed by evaporation underreduced pressure. The residual material was separated by preparativehigh pressure liquid chromatography using a mixture of 65% hexane and35% acetone as a solvent. Eluting first wasbis-(2,4-dichlorophenoxy)-3-methylpyridine and eluting second was thedesired 3-((2,4-dichlorophenoxy)-1H-1,2,4-triazol-1-yl methyl)pyridinewhich after recrystallization from an ether-hexane mixture gave 6.0grams of a white solid which melted at 75.5°-78° C. (Compound 1)

Example II 2-((4-Chlorophenoxy)-1H-1,2,4-triazol-1-yl methyl)thiophene##STR10##

A stirred mixture of 11.23 g (0.05 m) of 2-(4-chlorophenoxy)methylthiophene and 8.9 g (0.05 m) of N-bromosuccinimide (NBS) in 150 ml ofcarbon tetrachloride containing a catalytic amount (0.3 g) ofbenzoylperoxide was irradiated with a sun-lamp and heated with a heatgun until a vigorous exothermic reaction began. Irradiation wascontinued until all the NBS was used up, ˜3-5 minutes. The reactionmixture was immediately cooled to 10° C. in an ice-bath. The mixture wasfiltered to remove any insolubles. The filtrate was poured into astirred mixture of 3.45 g (0.05 m) of 1,2,4-triazole and 8.35 g (0.06 m)of powdered potassium carbonate in 300 ml of tetrahydrofuran. Themixture was stirred, at room temperature, for one hour and then filteredand solvent was removed by evaporation under reduced pressure. Theresidue was purified by preparative high pressure liquid chromatographyusing a mixture of 80% hexane and 20% acetone as the solvent. The secondpeak to elute was collected and the solvent was removed therefrom byevaporation under reduced pressure. The desired2-((4-chlorophenoxy)-1H-1,2,4-triazol-1-yl methyl)thiophene wasrecovered in a yield of 6.0 g (41% of theoretical). Recrystallization ofthe product from an ether-pentane mixture and cooling the mixture tominus (-) 20° C. gave colorless needles which melted at 111°-112.5° C.(Compound 2)

By following the procedures as set forth in the above examples, andemploying the appropriate reactants, the following compounds in Table Iare prepared.

    TABLE I      ##STR11##      Compound No. R R.sup.1 R.sup.2 R.sup.3 Y Physical Data      3 H     ##STR12##      ##STR13##      ##STR14##      O MP 72°-75° C.      4 H     ##STR15##      ##STR16##      ##STR17##      O n.sub.d.sup.25 = 1.5946      5 H     ##STR18##      ##STR19##      ##STR20##      O MP 77°-80° C.      6 H     ##STR21##      ##STR22##      ##STR23##      O Oil      7 H     ##STR24##      ##STR25##      ##STR26##      O      8     ##STR27##      ##STR28##      ##STR29##      ##STR30##      S      9 H     ##STR31##      ##STR32##      ##STR33##      O MP 67°-74° C.      10 H     ##STR34##      ##STR35##      ##STR36##      O MP 93°-94.5° C.      11 H     ##STR37##      ##STR38##      ##STR39##      O MP 82°-84° C.      12 H     ##STR40##      ##STR41##      ##STR42##      O Oil      13     ##STR43##      ##STR44##      ##STR45##      ##STR46##      S      14     ##STR47##      ##STR48##      ##STR49##      ##STR50##      S      15 H     ##STR51##      ##STR52##      ##STR53##      O MP 130°-132° C.      16 H     ##STR54##      ##STR55##      ##STR56##      O MP 91°-94° C.      17 H     ##STR57##      ##STR58##      ##STR59##      O MP 106°-109° C.      18 H     ##STR60##      ##STR61##      ##STR62##      O MP 100°-102° C.      19     ##STR63##      ##STR64##      ##STR65##      ##STR66##      O      20 H     ##STR67##      ##STR68##      ##STR69##      O MP 125.5°-126.5° C.      21 H     ##STR70##      ##STR71##      ##STR72##      O tan solid      22 H     ##STR73##      ##STR74##      ##STR75##      O MP 86°-89° C.      23 H     ##STR76##      ##STR77##      ##STR78##      O MP 95°-98° C.      24     ##STR79##      ##STR80##      ##STR81##      ##STR82##      S      25     ##STR83##      ##STR84##      ##STR85##      ##STR86##      S      26 H     ##STR87##      ##STR88##      ##STR89##      O MP 86.5°-88° C.      27 H     ##STR90##      ##STR91##      ##STR92##      O MP 116°-118° C.      28 H     ##STR93##      ##STR94##      ##STR95##      O MP 124°-127° C.      29 H     ##STR96##      ##STR97##      ##STR98##      O MP 96°-99° C.      30 H     ##STR99##      ##STR100##      ##STR101##      O MP 161°-163° C.      31 H     ##STR102##      ##STR103##      ##STR104##      O MP 87°-89° C.      32 H     ##STR105##      ##STR106##      ##STR107##      O MP 97°-98.5° C.      33 H     ##STR108##      ##STR109##      ##STR110##      O MP 163°-165° C.      34 H     ##STR111##      ##STR112##      ##STR113##      O MP 119°-121° C.      35 H     ##STR114##      ##STR115##      ##STR116##      O MP 67°-70° C.      36     ##STR117##      ##STR118##      ##STR119##      ##STR120##      S      37 H     ##STR121##      ##STR122##      ##STR123##      O MP 84°-87.5° C.      38     ##STR124##      ##STR125##      ##STR126##      ##STR127##      S      39 H     ##STR128##      ##STR129##      ##STR130##      O Oil      40     ##STR131##      ##STR132##      ##STR133##      ##STR134##      S      41 H     ##STR135##      ##STR136##      ##STR137##      O MP 110.5°-112° C.      42 H     ##STR138##      ##STR139##      ##STR140##      O MP 71°-73° C.      43 H     ##STR141##      ##STR142##      ##STR143##      O MP 86°-88° C.      44     ##STR144##      ##STR145##      ##STR146##      ##STR147##      O MP 108°-109.5° C.      45     ##STR148##      ##STR149##      ##STR150##      ##STR151##      O MP 87.5°-89.5° C.      46     ##STR152##      ##STR153##      ##STR154##      ##STR155##      S      47     ##STR156##      ##STR157##      ##STR158##      ##STR159##      O      48     ##STR160##      ##STR161##      ##STR162##      ##STR163##      O      49     ##STR164##      ##STR165##      ##STR166##      ##STR167##      S      50     ##STR168##      ##STR169##      ##STR170##      ##STR171##      O Gum      51     ##STR172##      ##STR173##      ##STR174##      ##STR175##      S      52     ##STR176##      ##STR177##      ##STR178##      ##STR179##      S      53 H     ##STR180##      ##STR181##      ##STR182##      O      54     ##STR183##      ##STR184##      ##STR185##      ##STR186##      O      55 H     ##STR187##      ##STR188##      ##STR189##      O      56     ##STR190##      ##STR191##      ##STR192##      ##STR193##      O      57 H     ##STR194##      ##STR195##      ##STR196##      O      58 H     ##STR197##      ##STR198##      ##STR199##      O      59 H     ##STR200##      ##STR201##      ##STR202##      O      60 H     ##STR203##      ##STR204##      ##STR205##      O      61 H     ##STR206##      ##STR207##      ##STR208##      O

PREPARATION OF STARTING MATERIALS

The dihalomethyl compounds corresponding to the formula ##STR209##wherein R and R¹ are as hereinbefore defined and A is chloro or bromoand which are employed as starting materials, are known compounds andcan be prepared by a variety of procedures.

In one such procedure for preparing compounds wherein A is bromine, onemole of an appropriate aromatic methyl compound of the formula##STR210## is reacted with 2 moles of a brominating agent such asN-bromosuccinimide (NBS) in the presence of a catalyst and a solvent.This reaction can be carried out employing the same procedures andconditions as set forth for step 1 of Method B.

Example III 4-Chloro-α,α-dibromotoluene ##STR211##

A mixture of 25.32 g (0.2 m) of 4-chlorotoluene, 71.2 g (0.4 m) of NBS,1.0 g of benzoylperoxide and 700 ml of carbon tetrachloride was heatedat reflux until all the NBS had been consumed (˜3-4 hours). Analysisshowed the mixture to be composed of mono, di and tribrominatedmaterial. An additional 15.0 g of NBS was added and heating wascontinued until it was consumed. Analysis indicated the product tocontain ˜7 percent monobrominated material, ˜14 percent tribrominatedmaterial and the desired dibrominated material. The mixture wasdistilled through a 5-plate Oldershaw column to give 25 g (44 percent oftheoretical) of the desired 4-chloro-α,α-dibromotoluene which boiled at64°-66° C. at 0.01 millimeter of mercury.

Those compounds wherein R and R¹ are both phenyl are known compounds astaught in U.S. Pat. No. 3,755,345 or those compounds which are unknowncan be prepared employing analogous methods.

Those compounds wherein R is hydrogen and R¹ is pyridyl are knowncompounds and can be prepared as taught in U.S. Pat. No. 4,260,766 andthe patents cited therein. The pyridine compounds which are substitutedwith nitro or trifluoromethyl groups can be prepared as indicated aboveemploying the appropriate starting materials.

The bromomethyl compounds corresponding to the formula ##STR212##wherein R and R¹ are as hereinbefore defined and which are employed asstarting materials, are known compounds and can be prepared by a varietyof procedures.

The arylmethyl compounds corresponding to the formula ##STR213## can beprepared by the reaction of substantially equimolar amounts of abromomethyl compound of the formula ##STR214## and a phenol, thiophenol,pyridinol or thiopyridinol corresponding to the formula

    YR.sup.2

in the presence of a solvent and an HBr absorber.

The reaction scheme is as follows: ##STR215## wherein R, R¹, R² and Yare as hereinbefore defined. No attempt has been made to present abalanced equation.

In carrying out this reaction, the reactants are mixed together in anysuitable fashion. Preferably, the phenol reactant is employed in slightexcess to insure completion of the reaction. Representative solventsinclude, acetonitrile, acetone, DMF, or DMSO. Representative HBrabsorbers include sodium and potassium carbonate, triethylamine,2,6-dimethylpyridine or DBN. The reaction mixture is stirred and heatedat reflux for about 15 minutes to about 6 hours. At the completion ofthe reaction, the solvent is removed and the residue diluted with water.The mixture is extracted with a solvent such as methyl ether, methylenechloride, chloroform to toluene. The organic extract is washed with adilute sodium hydroxide solution followed by water and a saturatedsodium chloride solution and then dried. The product can be recovered bydistillation and can be further purified, if desired, by solventrecrystallization.

Example IV (4-Chlorophenoxy)methyl thiophene ##STR216##

To a solution of 51.75 g (0.29 m) of 2-bromomethylthiophene and 38.6 g(0.3 m) of 4-chlorophenol in 400 ml of acetonitrile was added, all atonce, 38.6 g of powdered potassium carbonate. The resulting mixture wasstirred and heated at reflux for one (1) hour. The solvent was removedby evaporation under reduced pressure and 400 ml of water was added tothe residue. The resulting aqueous mixture was extracted three timeswith 200 ml portions of ether. The organic extracts were combined andthen washed sequentially with 50 ml of a 10 percent sodium hydroxidesolution, 300 ml of water and 300 ml of a saturated sodium chloridesolution. The extracts were dried over magnesium sulfate and the solventremoved by evaporation under reduced pressure. The residue was an orangeoil which slowly solidified upon standing. Distillation of the residuegave a main fraction boiling at 96°-100° C. at 0.01 millimeter ofmercury. The crude product slowly crystallized and was purified byrecrystallization from hexane. The (4-chlorophenoxy)methylthiopeneproduct, a white solid, was recovered in a yield of 41 g (63 percent oftheoretical) and melted at 45°-47° C.

The Examples set forth above under the "Preparation of StartingMaterials" heading are given only as illustrations of the variouspreparations which can be employed and should not be considered aslimiting.

The compounds of the present invention are useful as pesticides and areparticularly effective for the kill of certain plants and the kill andcontrol of various plant fungal organisms and certain insect pests. Inaddition many of the compounds have been found to have plant growthregulation activity. In this latter capacity, plants may be stunted ortheir growth can increase.

In their use a pesticidal or pesticidally effective amount or a growthregulator effective amount of the active compound per se or acomposition incorporating said amount of the compound in admixture witha suitable inert carrier or adjuvant is used as the toxicant for contactwith the pest, its habitat or with the desired plants. The pesticidalamount, of course, is that quantity which elicits toxic mortality amongthe treated pests or which regulates the growth of the plants.Generally, such responses result by contacting the target pests, theirhabitat or the desired plants with a composition containing from 0.00001to 99 or more percent of the active compound in the total composition.Good results are achieved upon contact with a composition containingabout 1000 parts of the active compound per million by weight.

Suitable compositions include those which are in the form of liquidsolutions, liquid emulsifiable concentrates, and dust or granularpreparations. Such can be further diluted as and where appropriate withconvention diluents.

Liquid compositions containing the active compound are prepared bydissolving the active compound in a suitable inert organic solvent suchas acetone, toluene, xylene, methylene chloride, chlorobenzene, ethylether or petroleum distillates, or other liquid carriers, propellantsubstances or by dispersing the active compound in water with or withoutthe aid of a suitable surface acting dispersing agent such as can beprovided by ionic or nonionic dispersing and emulsifying agents.

The aqueous compositions may contain one or more water-immisciblesolvents for the active compounds. In such compositions, the carriercomprises an aqueous emulsion, that is, a mixture of water-immisciblesolvent, emulsifying agent and water. The choice of dispersing and/oremulsifying agent and the amounts thereof employed is dictated by thenature of the composition type and by the ability of the agent tofacilitate the dispersion of the active compound in the aqueous carrierto produce the desired composition. Dispersing and emulsifying agentswhich may be employed in the compositions include the condensationproducts of alkylene oxides with phenols and organic acids,alkylarylsulfonates, polyoxyethylene derivatives or sobitan esters,complex ether alcohols, mahogany soaps, and the like. In suchcompositions, the surface active agents are usually employed in theamount of from 1 to 20 percent by weight of the combined weight of thesurface active agent and the active compound.

In the preparation of dust compositions, the active compound isdispersed in and on a finely divided inert solid such as talcum, chalk,gypsum, and the like. In such operations, the carriers are mechanicallyground with the compounds or wet with a volatile organic solventsolution thereof. Similarly, dust compositions containing the compoundmay be prepared from bentonite, fuller's earth, attapulgite, and otherclays. Depending upon the proportions of ingredients, these dustcompositions may be employed as concentrates and subsequently dilutedwith additional solid surface acting dispersing agent or with talc,chalk, or gypsum and the like to obtain a desired amount of active agentin a composition adapted to be applied for pest control. Also, suchconcentrate dust compositions may be dispersed in water with or withoutthe aid of a dispersing agent to form spray mixtures.

Granular formulations are conveniently prepared by impregnations, suchas through simple mechanical mixing, of the active compound in apresized carrier, usually of the type hereinbefore set forth.

In practice, the active compound is distributed so as to provide contactof the target pest or plants with effective amounts of the activecompound. Such contact can be achieved through direct contact with theactive compound or by more indirect means such as by application to thehabitat. Thus, for example, the active compound hereof or a compositionthereof can be spread throughout the environs of the target host so asto both provide direct and indirect contact thereof with a toxic orpesticidally effective amount or plant growth regulatory amount of theactive compound or a composition containing said active compound so asto provide ultimate contact therewith.

Example V

Aqueous compositions (dispersion) of various azolomethanes were preparedby admixing one of the active ingredients, dissolved in a suitablesolvent, with a predetermined amount of a surfactant to give aqueousdispersions containing various predetermined amounts of one of thecompounds as the sole active toxicant.

These compositions were evaluated, as insecticides, for the control oftwo-spotted spider mites beet armyworm larvae, tobacco budworm larvae,tobacco budworm eggs (ovicidal effect), codling moth, peach aphid andleaf hoppers wherein the azolomethane was present in the composition inan amount of 400 parts of the compound per million parts of ultimatecomposition (ppm); and for Western spotted cucumber beetle and black cutworms wherein the azolomethane present in an amount of 25 parts of thecompound per million parts of the ultimate composition (ppm).

Test procedures were employed as follows:

Two-Spotted Spider Mites

Separate wild mustard plants were infested with 20 two-spotted spidermites and the plants sprayed with one of the dispersions to run off. Ina like manner, 20 two-spotted spider mites were placed on control plantsand the plants sprayed to run off with a solution containing only waterand surfactant. The plants were maintained under conditions conducive tothe growth of the plants and mites. After a period of two days, theplants were examined to determine the percent kill and control of themites.

Western Spotted Cucumber Beetle

Seventy-five grams of air-dried soil was placed in an 8-ounce container.To the soil was added sufficient volume of the above 400 ppm aqueousdispersion, to give various predetermined concentrations of the activeingredient in the soil on a soil-chemical basis. The treated soil wasair-dried and thoroughly mixed. To each treated container, and controlcontainers treated with water and surfactant alone, was added 0.5milliliter of an aqueous suspension of the eggs of the Western spottedcucumber beetle (WSCB) (70-80 eggs, 3-4 days old). Additional treatedsoil was used to cover the eggs and a sprouted corn seed was placed onthe soil and covered with additional treated soil. The containers werethereafter maintained under conditions conducive to the growth of theseeds and the hatching of the eggs (75°-80° F.). Ten to twelve daysafter treatment, the containers and the plants therein were examined todetermine the percent kill and control of the larvae from the hatchedeggs.

Beet Armyworm

Separate cotton plant leaves were thoroughly wetted briefly by dippinginto one of the dispersions and the wetted leaves placed in an openPetri dish and permitted to dry. After the leaves were dry, 5 livearmyworm larvae, approximately late second instar were placed in eachPetri dish. In identical operations, 5 live and late second instar beetarmyworm larvae were placed in control Petri dishes, the leaf thereinhaving been wetted with a solution containing only water and surfactant.The dishes were maintained under moist conditions conducive for thegrowth of the beet armyworm larvae for a period of about 5 days. At theend of the 5-day period, the dishes were examined to determine thepercent kill and control of the beet armyworm larvae.

Tobacco Budworm

Separate 3-inch disc cut from tobacco plant leaves were thoroughlywetted briefly by dipping into one of the dispersions and the wettedleaves placed in an open Petri dish and permitted to dry. After theleaves were dry, 5 live tobacco budworm larvae approximately late secondinstar were placed in each Petri dish. In identical operations, 5 livetobacco budworm larvae were placed in control Petri dishes, the leaftherein having been wetted with a solution containing only water andsurfactant. The dishes were maintained under moist conditions and at 80°F. conducive for the growth of the tobacco budworm larvae for a periodof about 2 days. At the end of the 2-day period, the dishes wereexamined to determine the kill and control of the tobacco budwormlarvae.

Codling Moth

Sheets containing egg masses of codling moths were pinned to apples andthe egg sheets and apples were drenched with one of the aqueousdispersions. Separate egg masses and apples were also treated with acontrol mixture containing only water and surfactant. The eggmasses/apples were incubated under conditions conducive to the hatchingof the eggs and the growth of the larvae therefrom. Ten days aftertreatment, the apples were examined for the presence of egg hatch andlarvae. Counts of the number of larval penetration in the treated fruitwere compared to the number present in the untreated control todetermine the percent control obtained with the test compounds.

Peach Aphid

Separate chili pepper plants were infested with 20 green peach aphidsand the plants sprayed with one of the dispersions to run off. In a likemanner, 20 green peach aphids were placed on control plants and theplants sprayed to run off with a solution containing only water andsurfactant. The plants were maintained under conditions conducive to thegrowth of the plants and aphids. After a period of two days, the plantswere examined to determine the percent kill and control of the greenpeach aphids.

In such test, it was determined that each of compounds 5, 59 and 60 gaveat least 50 percent kill and control of two-spotted spider mites; eachof compounds 31 and 58 gave 100 percent kill and control of black cutworms; compound 58 was found to give 100 percent kill and control ofbeet armyworm larvae; compound 41 was found to give 100 percent kill andcontrol of codling moth larvae; each of compounds 2, 7, 34, 57 and 59were found to give at least 75 percent kill and control of peach aphids;and each of compounds 10, 31 and 44 were found to give at least 50percent kill and control of leaf hoppers.

Example VI

Aqueous compositions of various azolomethanes were prepared by admixingone of the active ingredients, dissolved in a suitable solvent, with apredetermined amount of a surfactant to give aqueous dispersionscontaining various predetermined amounts of one of the compounds, as thesole active toxicant.

These compositions were evaluated for pre-emergent applications on plotsimmediately after they were seeded with crabgrass, morning glory,barnyard grass, cotton, pigweed, yellow foxtail and velvet leaf. Otherplots similarly seeded with the above plant species were treated withthe like compositions containing no toxicant to serve as control plots.The treating applications were carried out by drenching the soil withthe aqueous compositions to obtain a treating rate of 10.0 pounds peracre. Thereafter, the plots were maintained under conditions conducivefor good plant growth. Two weeks after treatment, the plots wereexamined to determine the percent plant growth and evaluated. Theresults of the examinations are set forth below.

In such test, it was determined that each of compounds 5, 9, 10, 17, 21,29, 34, 39, 55 and 60 were found to give at least 50 percent kill andcontrol of undesired cotton plants; each of compounds 2, 3, 7, 9, 17,18, 20, 21, 29, 34, 37, 39, 55 and 60 were found to give at least 50percent kill and control of pigweed plants; each of compounds 7, 12, 16,17, 18, 20, 34, 55, 58, 59 and 60 were found to give at least 60 percentkill and control of crabgrass plants; each of compounds 4, 12, 16, 17,18, 20, 34, 55, 58, 59 and 60 were found to give at least 50 percentkill and control of yellow foxtail plants; each of the compounds 7, 9,10, 17, 20, 34, 37, 39, 44, 55, 58, 59 and 60 were found to give atleast 50 percent kill and control of morning glory plants; each of thecompounds 3, 7, 9, 10, 17, 20, 33, 34, 37, 39, 59 and 60 were found togive at least 50 percent kill and control of velvet leaf plants; andeach of compounds 7, 18, 20, 45, 55 and 59 were found to give at least60 percent kill and control of barnyard grass plants.

Example VII

Aqueous compositions (dispersions) of various azolomethanes wereprepared by admixing one of the active ingredients, dissolved in asuitable solvent, with a predetermined amount of a surfactant to giveaqueous dispersions containing various predetermined amounts of one ofthe compounds, as the sole active toxicant.

These compositions were evaluated for the post-emergent control ofbarnyard grass, crabgrass, pigweed, yellow foxtail, cotton, morningglory and velvet leaf. In these evaluations, plots of the above plantspecies grown to a height of about 4 inches were used. Aqueous spraycompositions, each containing 4,000 parts of a givenaryl(aryloxy)azolomethane compound per million parts of ultimatecomposition, were prepared and each separate composition was applied toa separate plot. The application was made to the point of run-off andwas carried out with conventional spraying equipment. Other plots weresprayed with similar compositions containing no toxicant to serve ascontrols. Thereafter, the plots were maintained under conditionsconducive for plant growth. Two weeks after treatment, the plots wereexamined for plant growth and evaluated.

In such tests, it was determined that each of compounds 5, 9, 10, 17,21, 28, 34, 39 and 70 were found to give at least 60 percent kill andcontrol of undesired cotton plants; each of compounds 3, 7, 9, 17, 18,20, 21, 28, 34, 37, 55 and 60 were found to give at least 60 percentkill and control of pigweed plants; each of compounds 5, 7, 12, 16, 17,18, 20, 34, 55, 58, 59 and 60 were found to give at least 70 percentkill and control of crabgrass plants; each of compounds 4, 12, 16, 17,18, 20, 34, 55, 58, 59 and 60 were found to give at least 50 percentkill and control of yellow foxtail plants; each of compounds 5, 7, 9,10, 17, 18, 34, 37, 39, 44, 55, 58, 59 and 60 were found to give atleast 50 percent kill and control of morning glory plants; each ofcompounds 3, 5, 7, 9, 10, 17, 20, 33, 34, 37, 39, 59 and 60 gave atleast 50 percent kill and control of velvet leaf plants; and each ofcompounds 7, 18, 20, 45, 58 and 59 gave at least 60 percent kill andcontrol of barnyard grass plants.

Example VIII

Aqueous compositions (dispersions) of various azolomethanes wereprepared by admixing one of the active ingredients, dissolved in asuitable solvent, with a predetermined amount of a surfactant to giveaqueous dispersions containing various predetermined amounts of one ofthe compounds as the sole active toxicant.

The compositions were evaluated, as fungicides, for the control of grapedowny mildew and apple powdery mildew wherein the azolomethane waspresent in the composition in an amount of 500 ppm; for the control ofapple scab wherein the azolomethane was present in an amount of 400 ppm;for Verticillium wilt wherein the azolomethane was present in an amountof 100 ppm; and for tobacco black shank and tobacco black root rotwherein the azolomethane was present in an amount of 25 ppm.

Test procedures were employed as follows:

Tobacco Black Shank

Soil infected with the tobacco black shank pathogen Phytophthoraparasitica var. nicotianeae was uniformly mixed and placed in 6-inchpots. To said pots were transplanted six week old tobacco seedlings ofthe "402" variety which had been grown in pathogen free soil. The testdispersions were employed to treat separate pots containing the seedlingby pouring 100 cubic centimeters of each of the test dispersions ontothe soil, assuring root contact with sufficient chemical. Additionalpots were treated with an aqueous acetone solution containing notoxicant to serve as controls. After treatments, the plants weremaintained under conditions conducive for good plant growth. Nineteendays after treatment, the plants were examined for disease control.

Apple Powdery Mildew

The test compositions were drenched onto soil in which apple plantseedlings were growing. One week later, the plant foliage was sprayedwith a suspension of spores of apple powdery mildew (Podosphaeraleucotricha). When disease symptoms on control plants developed,evaluation of percent control of plants in treated pots was made.

Apple Scab

The foliage of apple tree seedlings was sprayed to run off withsolutions of compounds of the invention prepared as described above.Four days after the treatment, the plants were innoculated with sporesof Venturia inaequalis. One week after the innoculation, the percentcontrol of apple scab disease was determined.

Tobacco Black Root Rot

Tobacco plant seedlings were transplanted into 2-inch (5 cm) diameterpots containing soil infested with tobacco black root rot (Thielaviopsisbasicola). Immediately after transplanting, the pots were drenched with40 ml of one of the test dispersions, two pots per dilution. Controlpots were drenched with acetone solution containing no test compound.The pots were maintained at a temperature of 60° F. and (15.5° C.) andwatered daily. The test was evaluated by estimating the percentage ofroot system that was injured, the evaluation being made when roots ofplants in the control pots showed 98 percent injury.

Grape Downy Mildew

The underside of the leaves of grape seedlings (cv. Carignane) at the3-4 leaf stage were sprayed with an aqueous suspension of the testmaterial. After application, the underside of the plant leaves weresprayed with a spore suspension of Plasmopara viticola in distilledwater. The plants were held in an infection chamber at 20° to 22° C. and100% r.h. for 7-8 days. When the disease symptoms were well developed,the seedlings were graded for disease control by rating seedlings,treated with the above solution (suspension) less toxicants, as `nocontrol` and treated plants with the absence of disease symptoms as`100% control`.

Verticillim Wilt

Soil infected with the vascular wilt organism Verticillim albo-atrum wasuniformly mixed and used to fill 6-inch pots to within 31/2 inches fromthe top. The pots were treated with aqueous dispersions of the testcompound. Additional infected soil was added to the pots to within 11/4inch of the top. Five cotton seeds were planted in each pot and the potswere watered lightly. Sterile soil was added to the pots to cover theseeds. Additional pots were also prepared as above except they were nottreated with chemical to serve as controls. The pots were thereaftermaintained under conditions conducive to good plant growth. Eight weeksafter treatment, the pots were examined to determine the percent ofdisease control.

In such test, it was determined that each of compounds 2, 3, 5, 6, 7, 9,10, 11, 12, 15, 17, 20, 21, 28, 29, 31, 42, 43, 57 and 60 were found togive at least 50 percent kill and control of causative organisms ofbarley powdery mildew; each of compounds 2, 7, 21, 28, 29, 33, 34 and 57were found to give at least 75 percent kill and control of the causativeorganism of wheat leaf rust; each of compounds 4, 5, 6, 20, 21, 29, 30,43, 57 and 58 were found to give 100 percent kill and control of thecausative organism of verticillium wilt; each of compounds 2, 7, 15, 34,42, 44, 57 and 61 were found to give at least 50 percent kill andcontrol of the causative organism of grape downy mildew; each ofcompounds 3, 7, 12, 15, 16, 21, 30, 31, 32, 39, 41, 57 and 60 were foundto give at least 75 percent kill and control of the causative organismof apple scab; each of compounds 2, 3, 5, 6, 7, 9, 10, 11, 12, 15, 17,18, 21, 31, 35, 37, 39, 42, 43, 44, 45, 57, 58, 59 and 60 were found togive at least 50 percent kill and control of the causative organism ofapple powdery mildew; and each of compounds 2, 3, 4, 5, 18, 44, 60 and61 were found to give 100 percent kill and control of the causativeorganism of tobacco black root rot.

Example IX

Tests were conducted to determine the effectiveness of the testcompositions in increasing the growth enhancement as evidenced by anincrease in the dry weight of the roots of sugar beets.

Sugar beets were grown in a greenhouse in pots whose soil consisted of˜97 percent sand. When the plants were 21 days old, they were sprayed tothe point of run-off with various dilutions of aqueous solutions of thetest compositions. These solutions were prepared by dissolving apredetermined amount of one of the test compounds in a predeterminedamount of water containing 0.1 percent of a wetting agent. Untreatedplants were maintained as controls.

One month after treatment, the plants were removed from the soil and theroots removed from the plants. The roots were placed in a forced airoven at 60° C. until no moisture remained (48-72 hours). The dry weightof the roots were measured and the results calculated as a percent ofthe control.

                  TABLE II                                                        ______________________________________                                                Increase in dry weight of                                                     sugar beet roots as a                                                         percent of control                                                            dosage in PPM                                                         Compound  6           25        100                                           ______________________________________                                        16        14          N.A.*     13                                            42        46          25        26                                            45        27          31        14                                            ______________________________________                                         *N.A. = No increase in dry weight noted.                                 

Example X

Tests were conducted to determine the effectiveness of the testcompositions in regulating the growth of sugar beet plants as evidencedby the stunting of the plants.

Sugar beets were grown in a greenhouse in pots whose soil, consisted of˜97 percent sand. When the plants were 21 days old, they were sprayed tothe point of run-off with various dilutions of aqueous solutions of thetest compositions. These solutions were prepared by dissolving apredetermined amount of one of the test compounds in a predeterminedamount of water containing 0.1 percent of a wetting agent. Untreatedplants were maintained as controls.

One month after treatment, the plants were examined to determine thedegree of stunting which occurred. Stunting of sugar beet plants wasbased on whether at least a 20 percent reduction occurred in the lengthof the stem which holds the leaf and in the leaf area. The compoundswere rated as having a stunting activity index of 1 if the treatedplants were stunted at a treating dosage rate of 165 ppm; a stuntingactivity index of 2 if the treated plants were stunted at a treatingdosage of between 165 and 330 ppm and a stunting activity index of 3 ifthe treated plants were stunted at a treating dosage of between 330 and1000 ppm. In these tests, compounds 9, 16, 44, 45 and 57 were found tohave a stunting activity of 1; compounds 1, 5, 7, 10, 11, 12, 17, 21,41, 42, 58 and 59 were found to have a stunting activity of 2 andcompounds 3, 4, 6, 15, 20, 31, 32, 33, 35, 39 and 43 were found to havea stunting activity of 3.

What is claimed is:
 1. A compound corresponding to the formula##STR217## wherein R represents phenyl or phenyl substitutedindependently with from 1 to 3 bromo, chloro, fluoro, iodo, C₁ -C₄alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃ groups;R¹ represents phenyl orphenyl substituted independently with from 1 to 3 bromo, chloro, fluoro,iodo, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃ groups; R² representsphenyl or phenyl substituted independently with from 1 to 3 bromo,chloro, fluoro, iodo, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃groups; R³ represents a 5-membered N-heterocyclic ring of the formula##STR218## wherein each Z independently represents --CH or N and atleast one of Z is N;X is C₁ -C₄ alkyl, Br, Cl, F or I and n representsan integer of from 0 to 3 and Y is oxygen or sulfur.
 2. A pesticidalcomposition which comprises an inert adjuvant in admixture with apesticidally effective amount of a compound corresponding to the formula##STR219## wherein R represents phenyl or phenyl substitutedindependently with from 1 to 3 bromo, chloro, fluoro, iodo, C₁ -C₄alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃ groups;R¹ represents phenyl orphenyl substituted independently with from 1 to 3 bromo, chloro, fluoro,iodo, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃ groups; R² representsphenyl or phenyl substituted independently with from 1 to 3 bromo,chloro, fluoro, iodo, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃groups; R³ represents a 5-membered N-heterocyclic ring of the formula##STR220## wherein each Z independently represents --CH or N and atleast one of Z is N;X is C₁ -C₄ alkyl, Br, Cl, F or I and n representsan integer of from 0 to 3 and Y is oxygen or sulfur.
 3. A method for thekill and control of fungal or insect pest which comprises contactingsaid pest with a pesticidally effective amount of a composition whichcomprises an inert adjuvant in admixture with a compound correspondingto the formula ##STR221## wherein R represents phenyl or phenylsubstituted independently with from 1 to 3 bromo, chloro, fluoro, iodo,C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃ groups;R¹ represents phenylor phenyl substituted independently with from 1 to 3 bromo, chloro,fluoro, iodo, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃ groups; R²represents phenyl or phenyl substituted independently with from 1 to 3bromo, chloro, fluoro, iodo, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃groups; R³ represents a 5-membered N-heterocyclic ring of the formula##STR222## wherein each Z independently represents --CH or N and atleast one of Z is N;X is C₁ -C₄ alkyl, Br, Cl, F or I and n representsan integer of from 0 to 3 and Y is oxygen or sulfur.
 4. A method forregulating the growth of plants which comprises contacting said plantswith a plant growth regulating amount of a composition which comprisesan inert adjuvant in admixture with a compound corresponding to theformula ##STR223## wherein R represents phenyl or phenyl substitutedindependently with from 1 to 3 bromo, chloro, fluoro, iodo, C₁ -C₄alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃ groups;R¹ represents phenyl orphenyl substituted independently with from 1 to 3 bromo, chloro, fluoro,iodo, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃ groups; R² representsphenyl or phenyl substituted independently with from 1 to 3 bromo,chloro, fluoro, iodo, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NO₂, CN or CF₃groups; R³ represents a 5-membered N-heterocyclic ring of the formula##STR224## wherein each Z independently represents --CH or N and atleast one of Z is N;X is C₁ -C₄ alkyl, Br, Cl, F or I and n representsan integer of from 0 to 3 and Y is oxygen or sulfur.